Process of removing ions from solutions using a complex with sulfur-containing hydrocarbons

ABSTRACT

A method for the removal and concentration of desired ions such as Pd(II), Ru(III), Pd(IV), Au(III), Au(I), Ag(I), and Hg(II) from a multiple ion source solution which may contain larger concentrations of other undesired ions including H +   comprises bringing the source solution into contact with a compound comprising a sulfur and electron withdrawing group containing ligand covalently bonded through an organic spacer silicon grouping to a solid inorganic support. The sulfur and electron withdrawing group containing ligand portion(s) of the compound has an affinity for the desired ions to form a complex thereby removing the desired ions from the source solution. The desired ions are removed from the compound by contacting the compound with a much smaller volume of a receiving solution having a greater affinity for the desired ions than does the sulfur and electron withdrawing group containing ligand portion of the compound. The process is useful in removing desired or unwanted ions from acidic waste streams, metal refining streams, and other industrial or environmental streams. The invention is also drawn to the sulfur and electron withdrawing group containing ligands covalently bonded through a spacer grouping to a hydrophilic inorganic solid support material.

FIELD OF THE INVENTION

This invention relates to sulfur-containing hydrocarbons which alsocontains electron withdrawing groups covalently bonded to a silane, suchas a trialkoxysilane, and to such intermediate compounds which arecovalently bonded to hydrophilic solid supports and to processes forremoving, separating and concentrating certain desired ions fromsolutions wherein such ions may be admixed with other ions which may bepresent in much higher concentrations by the use of suchsulfur-containing hydrocarbons containing electron withdrawing groupsbonded to such solid supports. More particularly, this invention relatesto a process for removing such ions from an admixture with others insolution by forming a complex of the desired ions with compoundscomposed of sulfur-containing hydrocarbons containing electronwithdrawing groups bonded to such solid supports by flowing suchsolutions through a column packed with such sulfur-containinghydrocarbons containing electron withdrawing group solid supportedmaterials and then selectively breaking the complex of the desired ionfrom the compounds to which such ion has become attached by flowing areceiving liquid in much smaller volume than the volume of solutionpassed through the column to remove and concentrate the desired ions insolution in the receiving liquid. The concentrated ions thus removed maythen be recovered by known methods.

BACKGROUND OF THE INVENTION

Effective methods for the recovery and/or separation of particular ionssuch as ruthenium, palladium, gold, silver, and mercury ions in eithercation or complex anion form from solutions thereof, admixed withchelating agents and/or other ions which may be present, represent areal need in modern technology. As specific examples, efficient andeconomical separation of (1) small amounts of Ru, Pd, Au, Ag, fromindustrial concentrates; (2) separation of Ru, Pd, Au, and Ag, fromsolutions containing large amounts of base metals; and (3) separation ofHg as toxic wastes from acidic solutions, all represent real separationneeds with presently either unsatisfactory technologies for theiraccomplishment, or for which more economical technologies are desired.These ions are often present at low concentrations in solutionscontaining other ions at much greater concentrations. Hence, there is areal need for a process to selectively concentrate and recover theseions.

The fact is known that macrocyclic polythioethers and certain othersulfur-containing hydrocarbon ligands present as solutes in a solventsuch as water are characterized by their ability to selectively formstrong bonds with the noble metal, platinum group metal, and mercuryions or groups of these ions present as solutes in the same solvent asdescribed in articles by R. M. Izatt, et al. A CALORIMETRIC TITRATIONSTUDY OF UNI-AND BIVALENT METAL ION INTERACTION WITH SEVERAL THIADERIVATIVES OF 9-CROWN-3, 12-CROWN-4, 15-CROWN-5, 18-CROWN-6, 24-CROWN-8AND WITH SEVERAL OXATHIAPENTADECANES IN WATER OR WATER-METHANOL SOLVENTSAT 25° C., Inoroanica Chemica Acta. 30:1-8 (1978) for the complexationof silver and mercury ions by open chain sulfur-containing hydrocarbonsand by S. R. Cooper, CROWN THIOETHER CHEMISTRY, Accounts of ChemicalResearch. 21:141-146 (1988) for the complexation of rhodium and silverions by macrocyclic sulfurcontaining ligands.

Articles such as those entitled SILANE COMPOUNDS FOR SILYLATING SURFACESby E. P. Plueddemann, in "Silanes, Surfaces and Interfaces Symposium,Snowmass, 1985," Ed. by D. E. Leyden, Gordon and Breach, publishers, pp.1-25 (1986) and SILANE COUPLING AGENTS by E. P. Plueddemann, PlenumPress, pp. 1-235 (1982) list many different types of organic materialswhich have been attached to silane compounds and discuss some of theirproperties.

Bradshaw, et al., U.S. Pat. No. 4,959,153 describe certain sulfurcontaining hydrocarbons covalently bonded to a hydrophilic solid supportwhich can be used to selectively bind noble and platinum group metals aswell as some transition metals. In many cases these prior artsulfur-containing hydrocarbons can be eluted using one or two eluentssuch as amines or CN⁻ which are not always desirable eluents.

These prior art compositions do not provide the means for selecting thedesired interactive strength between the ions to be removed and theligands to which they are to be bound for removal. Hence the sought forselectivity for ion removal and subsequent elution from the bindingligands is not always achieved.

The compositions described herein accomplish these desirable objectivesby a controlled reduction of the interaction strength via theappropriate addition of electron withdrawing groups of varying strength.

SUMMARY OF THE INVENTION

The unique properties of the sulfur-containing plus electron withdrawinggroup containing compositions described herein often show greaterselectivity amongst the platinum and noble metals and also over thetransition metals than the materials in the prior art. Furthermore, thebinding strength of these new materials is sufficient to remove ionssuch as Ru, Pd, Au, Ag, and Hg in many matrices even when present atvery low levels and subsequently elute the purified Ru, Pd, Au, Ag, Hg,or other ions using a variety of aqueous eluents such as NO₂ ⁻, SO₃ ²⁻,EDTA, DTPA, NTA, Br and I⁻ as well as NH₃, amines, thiourea and CN⁻.Those indicated as ions may be used in acid or salt form. Therefore,sulfur-containing plus electron withdrawing hydrocarbon ligands asattached to appropriate inorganic solid supports form the basis of thepresent invention. The compounds, methods of synthesis and propertiesare described below. The invention also encompasses processes for usingthe compounds for the separation of desired ions.

The compounds of the present invention comprise suitable sulfurcontaining electron withdrawing ligands which are covalently bondedthrough a spacer grouping to a silicon atom and further covalentlybonded to a solid support.

The intermediate groups comprise sulfur-containing hydrocarbons whichalso contain electron withdrawing groups covalently bonded to a silaneand are represented by the following Formula 1: ##STR1## wherein L is amember independently selected from the group consisting of Cl, Br, I,alkyl, alkoxy, substituted alkyl or substituted alkoxy. When L is notalkoxy it is classified as a leaving group. M can be either L or--X--A--Q. Preferably L will be methoxy. X is any suitable spacer groupwhich allows the A--Q group to be unencumbered when attached to a solidsupport. X can be any spacer member selected from the group consistingof either (1) groups having the formula:

    (CH.sub.2).sub.a (OCH.sub.2 CHR.sup.1 CH.sub.2).sub.b

wherein R¹ is a member selected from the group consisting of H, SH, OH,lower alkyl, and aryl, such as phenyl, naphthyl and pyridyl; a is aninteger from 2 to about 10; b is an integer of 0 or 1; (2) phenylene or(3) is a methacryl group. Preferably X is a glycidoxypropyl group wherea is 3, b is 1 and R¹ is OH. A is a member selected from the groupconsisting of S, 0, NR², and CH₂, wherein R² is a member selected fromthe group consisting of H and lower alkyl with the proviso that A mustbe S if Q does not contain an S atom and A must be CH₂ when Ar is2-furyl, 2-thienyl or 2-pyrryl. A is preferably S. Q is a memberselected from the group consisting of Ar or a lower alkyl. Ar is an arylgroup selected from the group consisting of phenyl, thiophenyl,naphthyl, biphenyl, pyridyl, pyrimidinyl, pyrazyl, pyridazinyl, furyl,thienyl, pyrryl, quinolinyl and bipyridyl. The Ar groups are inthemselves electron withdrawing and may be unsubstituted. However, thelower alkyl groups must contain electron withdrawing substituents unlessthe X group is phenylene. Both the Ar and lower alkyl groups may containelectron withdrawing groups selected from the group consisting of amido,aldehyde, ketone, sulfonyl, carboxyl, benzene, I, Br, Cl, F, cyano andnitro and mixtures thereof. When Q is Ar these groups can, if desired,be separated from the Ar group by an alkyl spacer which may lessen theelectron withdrawing capability. Further, the Ar rings and lower alkylgroups can be entirely substituted if desired, e.g. Ar could be2,3,4,5,6 pentachlorobenzene with A being S and a halo group separatedfrom Ar by an alkyl spacer could be a perhalo group. The A--Q group mustcontain at least one S atom and, when Q is Ar, preferably one or more ofthe above named substituents will be present as they are electronwithdrawing groups and serve to regulate the log K value between thesulfur and the metal ion being concentrated or removed. By controllingthe electron density at the sulfur, the binding capacity and selectivityof the A--Q ligand can be regulated. As stated above, when furyl,thienyl, pyrryl are attached to the A group via their 2 position the Agroup must be CH₂. The term lower alkyl refers to alkyl groups havingfrom 1 to 6 carbon atoms.

The compositions used for the concentration and/or separation of the Au,Ag, Pd, Ru and Hg ions are made by reacting a Formula I compound with asolid matrix selected from the group consisting of sand, silica gel,glass, glass fibers, alumina, zirconia, titania and nickel oxide orother hydrophilic inorganic supports and mixtures thereof to form acompound of Formula II: ##STR2## wherein X, A and Q have the meaningsgiven above, Matrix is a member selected from the group consisting ofsand, silica gel, glass, glass fibers, alumina, zirconia, titania andnickel oxide or other hydrophilic inorganic supports and mixturesthereof and y and Z are each members selected from the group consistingof O-Matrix, L or --X--A--Q. When y and Z moieties L they arefunctionally classified as leaving groups, i.e. groups attached to thesilicon atom which, when reacted with an 0-solid hydrophilic matrixmaterial, may leave or be replaced by the 0-Matrix. If any suchfunctional leaving groups are left over after reacting a siliconcontaining spacer group or spacer/ligand group with the solidhydrophilic matrix support material, these groups will have no directfunction in the interaction between the desired ion and the sulfurcontaining electron withdrawing A--Q hydrocarbon ligand attached to thesolid support.

As referred to above, X is a spacer grouping which is of a functionalnature that it is sufficiently hydrophilic to function in an aqueousenvironment and will separate the ligand from the solid matrix supportsurface to maximize the interaction between the ligand and desired ionbeing separated. Representative of X are members such asglycidoxypropyl, ethyl, propyl, phenyl and methacryl.

The ligands used in the present invention, combining the presence ofsulfur and electron withdrawing groups, wherein the ligands arecovalently bonded via a spacer grouping to solid supports as shown inFormula II are characterized by high selectivity for and removal ofdesired ions or groups of desired ions such as Pd⁴⁺, Pd²⁺, Ru³⁺, Au³⁺,Au⁺, Ag⁺, and Hg²⁺, even when present at low concentrations, from thesource phase solution containing a mixture of these metal ions with theions one does not desire to remove (i.e. referred to as "undesiredions") present in much greater concentrations in the solution. Theseparation is accomplished, even in the presence of other complexingagents or matrix constituents, particularly acids, in a separationdevice, such as a column, through which the solution is flowed. Theprocess of selectively removing and concentrating the desired ion(s) ischaracterized by the ability to quantitatively complex from a largervolume of solution the desired ion(s) when they are present at lowconcentrations. The desired ions are recovered from the separationcolumn by flowing through it a small volume of a receiving phase whichcontains a solubilizing reagent which need not be selective, but whichwill strip the desired ions from the ligand quantitatively Otherequivalent apparatus may be used instead of a column, e.g., a slurrywhich is filtered, washed with a receiving liquid to break the complexand recover the desired ion. The recovery of the desired metal ions fromthe receiving phase is readily accomplished by known procedures.

As previously stated, Bradshaw et al., U.S. Pat. No. 4,959,153 teachthat sulfur-containing hydrocarbons covalently bonded to a hydrophilicsolid support without electron withdrawing group(s) can be used toselectively bind noble and platinum group metals as well as sometransition metals. However, the sulfurcontaining plus electronwithdrawing groups of the present invention often show greaterselectivity amongst the platinum and noble metal groups, i.e. Au, Ag, Pdand Ru and also over some transition metals, i.e. Hg, than the materialsin the '153 patent. Furthermore, the binding strength of the ligands ofthe present invention is sufficient to remove ions such as Ru, Pd, Au,Ag, and Hg in many matrices even when present at very low levels andsubsequently elute the purified Ru, Pd, Au, Ag, Hg, or other ions usinga variety of eluents such as NO₂ ⁻, SO₃ ²⁻, EDTA, DTPA, NTA, Br. and I⁻as well as NH₃, amines, thiourea and CN⁻. In many cases thesulfur-containing hydrocarbon ligands, not containingelectron-withdrawing groups described previously by Bradshaw et al. canbe eluted using a limited number of eluents such as amines or CN⁻ whichare not always desirable eluents. The compositions described hereinaccomplish these desirable objectives by a controlled reduction of theinteraction strength between the ligand and the metal being removed viathe appropriate addition of the electron withdrawing groups.

Examples of electron withdrawing groups which can be used are the amido,aldehyde, ketone, sulfonyl, carboxyl, benzene, I, Br, Cl, F, cyano andnitro groups. These groups can, if desired, be separated from the Argroup by an alkyl spacer which, in the case of the halo substituents canresult in a perhaloalkyl group. More than one electron withdrawinggroups can also be added to perform a larger overall combined reductionof the interaction ability of the ligand. In general, the strength ofthe withdrawing groups increase in the order of amido, aldehyde, ketone,sulfonyl, carboxyl, benzene, I. Br, Cl, F, cyano and nitro. The use ofalkyl spacers may somewhat diminish the electron withdrawing capability.The stronger withdrawing groups are used to make greater reductions inthe interaction strength of the ligands. Positioning of the withdrawinggroups can also be used to control the interaction constant. Forexample, in adding monochloro substituted benzene withdrawing groups,the chloro group increases in withdrawal capability in the order ofmeta, ortho and para positions.

These parameters allow for myriad ligand combinations possessing avariety of interaction strengths to be synthesized for selective ionremoval. This further provides for ligand choices to be made for usewith a variety of eluents of varying selectivity and interactionstrength properties.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

As summarized above, the present invention is drawn to novel sulfur andelectron withdrawing group containing ligands covalently bound through aspacer to a silicon moiety as shown in Formula I and further to suchintermediate compounds attached to a solid matrix or support, as shownin Formula II. The invention is also drawn to the concentration andremoval of certain desired ions such as Pd⁴⁺, Pd²⁺, Ru³⁺, Au³⁺, Au⁺,Ag⁺, and Hg²⁺ from other ions. For example, effective methods ofrecovery and/or separation of metal ions from other metal ions, such as(1) the small amounts of Ru, Pd, Au and Ag from Rh and/or Irconcentrates; (2) separation of Pd, Ru, Au and/or Ag from solutionscontaining large amounts of base metals; and (3) separation of Hg astoxic wastes from acidic solutions represent a real need for which thereare no established procedures for satisfactory selective removal. Suchsolutions from which such ions are to be concentrated and/or recoveredare referred to herein as "source solutions." In many instances theconcentration of desired ions in the source solutions will be much lessthan the concentration of other or undesired ions from which they are tobe separated.

The concentration of desired ions is accomplished by forming a complexof the desired ions with a compound shown in Formula II by flowing asource solution containing the desired ions through a column packed witha Formula II compound to attract and bind the desired ions to the ligandportion of such compound and subsequently breaking the ligandcompound-complex by flowing a receiving liquid in much smaller volumethan the volume of source solution passed through the column to removeand concentrate the desired ions in the receiving liquid solution. Thereceiving liquid or recovery solution forms a stronger complex with thedesired ions than does the ligand portion of a Formula II compound andthus the desired ions are quantitatively stripped from the ligand inconcentrated form in the receiving solution. The recovery of desiredions from the receiving liquid is accomplished by known methods.

The sulfur and electron withdrawing group containing ligand compounds,as represented by Formulas I and II, may be prepared by various methodswhich are illustrated in the examples which follow. In each of theseexamples the silane and X or "spacer" combination is3-glycidoxypropyltrimethoxysilane resulting in an intermediate offollowing Formula III: ##STR3##

Also, in the following examples, a compound of Formula III, is reactedwith silica gel resulting in an --A--Q ligand bound through the3-glycidoxypropyltrimethoxysilane to a silica gel matrix having thegeneral Formula IV: ##STR4## wherein Y' and Z' are each members selectedfrom the group consisting of methoxy or O-Silica.

The following examples are given to illustrate compounds which have beenmade in accordance with Formula IV. These examples are illustrativeonly, and are not comprehensive of the many different compounds whichhave been or can be made within the scope of the present invention. Thesilica matrix can be replaced by various other solid supports and thespacer or X group can also be varied. Moreover, there are myriad --A--Qligands which may be utilized to take advantage of their selectivity fora desired ion.

EXAMPLE 1

In this example the A group is S and the Q group is phenyl. Thiophenol,as the ligand grouping, was attached to the surface of silica gel viaglycidoxypropyltrimethoxysilane in the following manner. First, 2 gramsof reagent grade thiophenol were dissolved in 10 mL of methanol in whichhad been dissolved 0.2 g of sodium metal. This mixture was slowly addedto a three-necked round bottom flask equipped with a mechanical stirrercontaining 20 mL of toluene and 4.3 g of3-glycidoxypropyltrimethoxysilane at 75° C. The reaction was allowed toproceed overnight thereby forming an intermediate corresponding toFormula III where A is S and Q is phenyl. To the intermediate was added18 g of silica gel (250-500 μ particles). Again the mixture was stirredand heated at 60-80° C. overnight. The final product was isolated byfiltration and dried before testing for capacity as a ligand forselective ion removal.

EXAMPLE 2

The procedure of Example 1 above was followed with the exception that4-chlorothiophenol was used in place of the thiophenol. In this Examplethe Cl atom was contained on the phenyl group as an electron withdrawingmoiety. The mole ratio of thiophenol to silane was kept at 1:1.02. Thefinal product was again filtered and dried thoroughly before testing.

EXAMPLE 3

The procedure of Example 2 above was followed except that the3-chlorothiophenol isomer was used as the reactant in place of the4-chlorothiophenol.

EXAMPLE 4

The procedure of Example 2 was again used except that 4-fluorothiophenolwas used as the reactant in place of the 4-chlorothiophenol therebyresulting in a composition where F is attached to the phenyl group as anelectron withdrawing moiety.

EXAMPLE 5

This example was the same as Example 2 above except that3,4-dichlorothiophenol was used as the reactant in place of the4-chlorothiophenol thereby resulting in a composition containing twoadjacent Cl atoms on the phenyl group as electron withdrawing moieties.

EXAMPLE 6

This example is the same as Example 2 above except that4-nitrothiophenol was used as the reactant in place of the4-chlorothiophenol thereby resulting in a NO₂ electron withdrawingmoiety on the phenyl group.

EXAMPLE 7

This example is the same as Example 2 above except that the isomeric2-chlorothiophenol was used as the reactant in place of the4-chlorothiophenol.

EXAMPLE 8

This example is the same as Example 5 except that 2,6-dichlorothiophenolwas used as the reactant in place of the 3,4-dichlorothiophenol.

EXAMPLE 9

This example is the same as Example 2 above except that2-mercaptopyrimidine was used as the reactant in place of the4-chlorothiophenol thereby resulting in a composition where A is S and Qis pyrimidinyl.

EXAMPLE 10

This example is the same as Example 2 except that 2-mercaptoacetic acidwas used as the reactant in place of the 4-chlorothiophenol therebyresulting in a composition where A is S and Q is CH₂ COOH, e.g. a methylgroup having a carboxyl electron withdrawing group attached.

EXAMPLE 11

This example is the same as Example 2 above except that thiosalicylicacid was used as the reactant in place of the 4-chlorothiophenol and thesolvent in this case was ethanol. Water was also added just before thesilica gel to increase the solubility of the intermediate. In thiscomposition A is S and Q is phenyl having a carboxyl group attached.

EXAMPLE 12

In this example a disubstituted silicon intermediate is prepared byreacting tetramethoxysilane with the Grignard reagent prepared from4-bromo-thioanisole and magnesium. The Grignard reagant is present at a2:1 ratio compared to the silane. This results in a disubstitutedsilicon intermediate which may be purified by distillation under highvacuum. The intermediate is then bonded to silica gel in the mannerdescribed above. This results in a composition according to Formula IIwherein Matrix is O-Silica, y is X--A--Q, wherein X is phenyl, A is Sand Q is methyl and Z is methoxy or O-Matrix. If desired Z can also be--X--A--Q by using a 3:1 ratio of Grignard reagent to silane.

METAL ION RECOVERY AND CONCENTRATION PROCESS

The process of selectively and quantitatively concentrating and removinga desired ion or group of desired ions present at low concentrationsfrom a plurality of other undesired ions in a multiple ion sourcesolution in which the undesired ions, along with acid(s) and otherchelating agents may be present at much higher concentrations, comprisesbringing the multiple ion containing source solution into contact with asulfur and electron withdrawing group containing ligand matrix supportedcompound as shown in Formula II which causes the desired ion(s) tocomplex with the sulfur and electron withdrawing group containing ligandportion of the compound and subsequently breaking or stripping thedesired ion from the complex with a receiving solution which forms astronger complex with the desired ions than does the sulfur and electronwithdrawing group containing ligand or which forms a stronger complexwith the sulfur and electron withdrawing group containing ligand. Thereceiving or recovery solution contains only the desired ions in aconcentrated form.

The sulfur and electron withdrawing group containing ligand solid matrixsupport functions to attract the desired ions (DI) according to FormulaV:

    (Matrix-O).sub.1-3 --Si--X--A--Q + DI→(Matrix-O).sub.1-3 --Si--X--A--Q:DI                                          (Formula V)

Except for DI, Formula V is an abbreviated form of Formula II or FormulaIV wherein A--Q stands for the sulfur and electron withdrawing groupcontaining ligand. DI stands for desired ion being removed. WhenMatrix-O is less than three the other positions are taken by y and Z orY' and Z' groups as described above.

Once the desired ions are bound to the sulfur and electron withdrawinggroup containing ligand, they are subsequently separated by use of asmaller volume of a receiving liquid according to Formula VI:

(Matrix-O)₁₋₃ --Si--X--A--Q:DI + RL→(Matrix-O)₁₋₃ --Si--X--A--Q + RL:DI(Formula VI)

where RL stands for the receiving liquid.

The preferred embodiment disclosed herein involves carrying out theprocess by bringing a large volume of the source multiple ion solution,which may contain hydrogen ions and may also contain chelating agents,into contact with a sulfur and electron withdrawing group containingligand-solid support compound of Formula II or IV in a separation columnthrough which the mixture is first flowed to complex the desired metalions (DI) with the sulfur and electron withdrawing group containingligand-solid support compound as indicated by Formula II or IV above,followed by the flow through the column of a smaller volume of areceiving liquid (RL), such as aqueous solutions of NO₂ ⁻, SO₃ ²⁻, EDTA,DTPA, NTA, Br⁻ and I⁻ as well as NH₃, amines, thiourea and CN⁻. Asspecific examples are aqueous K₂ SO₃, NH₃, EDTA, NaNO₂ and HBr, andothers which form a stronger complex with the desired ion than does thesulfur and electron withdrawing group containing ligand bound to thesolid support or forms a stronger complex with the sulfur and electronwithdrawing group containing ligand bound to solid support than does thedesired ion. In this manner the desired ions are carried out of thecolumn in a concentrated form in the receiving solution as indicated byFormula VI. The degree or amount of concentration will obviously dependupon the concentration of desired ions in the source solution and thevolume of source solution to be treated. The specific receiving liquidbeing utilized will also be a factor. The receiving liquid does not haveto be specific to the removal of the desired ions because no other ionswill be complexed to the ligand. Generally speaking the concentration ofdesired ions in the receiving liquid will be from 20 to 1,000,000 timesgreater than in the source solution. Other equivalent apparatus may beused instead of a column, e.g., a slurry which is filtered which is thenwashed with a receiving liquid to break the complex and recover thedesired ion(s). The concentrated desired ions are then recovered fromthe receiving phase by known procedures.

Illustrative of desired ions which have strong affinities for sulfur andelectron withdrawing group containing ligands bound to solid supportsare Pd(II), Ru(III), Pd(IV), Au(III), Au(I), Ag(I), and Hg(II). Thislisting of preferred ions is not comprehensive and is intended only toshow the types of preferred ions which may be bound to sulfur andelectron withdrawing group containing ligands attached to solid supportsin the manner described above. The affinity of the ligand to the ionswill obviously vary depending upon the ion and the ligand configuration.Hence it is possible that, even in the above listing, those ions havingthe stronger affinity for the ligand will be selectively removed fromother ions in the listing which have a weaker affinity for theparticular ligand. Hence, by proper choice of ligands and makeup of thesource solution it is also possible to separate and concentrate onedesired ion from another. Therefore, the terminology "desired ions" and"undesired ions" is relative and the ion having the stronger affinity tothe ligand will generally be the "desired" ion.

The process of the invention is particularly adaptable to the removal ofPd(II), Ru(III), Ag(I), Au(III), and/or Hg(II) ions from sourcesolutions from other metal ions in water supplies, waste solutions,deposits and industrial solutions and silver recovery from wastesolutions, e.g., from emulsions on photographic and X-ray film.

Removal of Desired Molecules With Ligand-Matrix Compounds

The following examples demonstrate how the sulfur and electronwithdrawing group containing ligand bound to a solid support compound ofFormula II or Formula IV may be used to concentrate and remove desiredions. The sulfur and electron withdrawing group containing ligandcontaining solid support compound is placed in a column. An aqueoussource solution containing the desired ion or ions, in a mixture ofother undesired ions and/or chelating agents which may be in a muchgreater concentration, is passed through the column. The flow rate forthe solution may be increased by applying pressure with a pump on thetop or bottom of the column or applying a vacuum in the receivingvessel. After the source solution has passed through the column, a muchsmaller volume of a recovery solution, i.e. an aqueous solution, whichhas a stronger affinity for the desired ions than does the ligand, ispassed through the column. This receiving solution contains only thedesired ion(s) in a concentrated form for subsequent recovery.

The following examples of separations and recoveries of ions by theinorganic support-bound sulfur and electron withdrawing group containingligands which were made as described in Examples 1 through 11 are givenas illustrations. These examples are illustrative only, and are notcomprehensive of the many separations of ions that are possible usingthe materials of Formula II. However, separation of other desired ionsmay be accomplished as in the following examples and the exact processor procedure to be followed can be readily determined by one skilled inthe art.

EXAMPLE 13

In this example, 2 grams of the silica gel-bound sulfur plus benzeneelectron withdrawing group containing ligand of Example 1 were placed ina column. A 1000 ml solution of 3 ppm Hg in 1 M aqueous HNO₃ was passedthrough the column using a vacuum pump. The column was then washed with25 ml of H₂ O to remove the HNO₃. Finally the Hg was eluted using 10 mlof 6M HCl. An analysis of the recovery solution by atomic absorptionspectroscopy (AA) showed that greater than 95% of the Hg originally inthe 1000 ml Hg solution was in the 10 ml recovery solution.

EXAMPLE 14

In this example, separate runs are made using 2 grams of the silica gelsulfur-containing hydrocarbon including the chlorobenzene electronwithdrawing groups of Examples 2, 3, 5, 7 and 8 The composition isplaced in a column and a 250 ml solution of 100 ppm Pd²⁺ in 9M aqueousHCl, 0.1M aqueous CuCl₂, 1M aqueous FeCl₃, 1000 ppm Pt²⁺ and 0.5Maqueous NiCl₂ is passed through the column using a vacuum pump toincrease the flow rate. The loading solution is washed out of the columnwith 25 ml of 0.1 M HCl being passed through the column. Then a 10 mlsolution of 0.5M aqueous K₂ SO₃ is passed through the column. Ananalysis of the recovery solution by inductively coupled plasmaspectroscopy (ICP) in each instance shows that greater than 99% of thePd²⁺ originally in the 250 ml Pd solution is in the 10 ml recoverysolution and that less than 1 ppm of Cu, Fe, Pt, or Ni is present in therecovery solution.

EXAMPLE 15

In this example 2 grams of the silica gel-bound sulfur plus nitrobenzeneelectron withdrawing group hydrocarbon of Example 6 are placed in acolumn. A 250 ml sample of the Pd, Cu, Fe, Pt and Ni containing solutionidentical to that in Example 13 is passed through the column. The columnis washed with 25 ml of 0.1M HCl and then eluted with 10 ml of 5 M HBr.ICP analysis of the recovery solution shows that greater than 99% of thePd from the original loading solution and less than 1 ppm, Cu, Fe, Pt,or Ni is present in the 10 ml recovery solution.

EXAMPLE 16

In this example, 2 grams of the silica gel-bond sulfur plus carboxylicacid electron withdrawing group hydrocarbon of Example 10 are placed ina column. A 1000 ml solution of 10 ppm, Ag⁺ in 5M HNO₃ is passed throughthe column using a vacuum pump. A 25 ml solution of H₂ O is passedthrough the column to wash the HNO₃ out. A 10 ml solution of 6 M HCl ispassed through the column. ICP analysis of the recovery solutionindicates greater than 95% of the Ag from the original solution is inthe 10 ml recovery solution.

EXAMPLE 17

In this example, 2 grams of the silica gel-bound sulfur plus carboxylicacid benzene electron withdrawing group containing hydrocarbon ofExample 11 are placed in a column. A 250 ml solution of 200 ppm Au(III)in 6M aqueous HCl is passed through the column. The column is washedwith 25 ml of H₂ O and the Au is then eluted using 10 ml of 5 M NaI.Analysis of the recovery solution by AA shows that greater than 99% ofthe Au originally in the 250 ml solution is in the 10 ml recoverysolution.

Although the invention has been described and illustrated by referenceto certain specific silica gel-bound sulfur and electron withdrawinggroup containing ligands falling within the scope of Formula II and theprocess of using them, other analogs of these sulfur and electronwithdrawing group containing ligand compounds also falling within thescope of Formula II are also within the scope of the invention as areprocesses of using them to separated and recover desired ions. Theinvention is therefore limited only in scope by the following claims andfunctional equivalents thereof.

We claim:
 1. A method of removing desired ions from a mixture thereof insolution with other ions said method comprising:(a) bringing saidsolution having a first volume into contact with a compound comprising asulfur and electron withdrawing group containing ligand-covalentlybonded via a silane spacer grouping to a solid support matrix having theformula: ##STR5## wherein (i) Matrix is a member selected from the groupconsisting of sand, silica gel, glass, glass fibers, alumina, zirconia,titania and nickel oxide and mixtures thereof,(ii) y and Z are membersindependently selected from the group consisting of (a) O-Matrix, (b)X--A--Q, or (c) Cl, Br, I, alkyl, alkoxy, substituted alkyl orsubstituted alkoxy; (iii) X can be any spacer member selected from thegroup consisting of (1) groups having the formula:

    (CH.sub.2).sub.a (OCH.sub.2 CHR.sup.1 CH.sub.2).sub.b

wherein R¹ is a member selected from the group consisting of H, SH, OH,lower alkyl, and aryl; a is an integer from 2 to about 10 and b is aninteger of 0 or 1, (2) phenyl and (3) methacryl; (iv) A is a memberselected from the group consisting of S, 0, NR², and CH₂, wherein R² isa member selected from the group consisting of H and lower alkyl withthe proviso that A must be S when Q does not contain an S atom; (v) Q isa member selected from the group consisting of Ar and lower alkyl withthe provisos that (1) Q must be electron withdrawing when X is otherthan phenyl (2) must contain an S atom when A does not and (3) whereinAr is an aryl group selected from the group consisting of phenyl,thiophenyl, naphthyl, biphenyl, pyridyl, pyrimidinyl, pyrazyl,pyridazinyl, furyl, thienyl, pyrryl, quinolinyl and bipyridyl; and (vi)with the further proviso that A must be CH₂ when Q is Ar selected fromthe group consisting of 2-furyl, 2-thienyl and 2-pyrryl; (b) removingsaid solution from contact with said compound to which said desired ionshave been complexed; and (c) contacting said compound having desiredions complexed thereto with a volume, smaller than said first volume, ofa receiving solution having either a greater affinity for said desiredions than said compound or a greater affinity for said compound thansaid desired ions thereby breaking said complex between said compoundand said desired ions and recovering the desired ions in concentratedform in said smaller volume of said receiving solution.
 2. A methodaccording to claim 1 wherein the desired ions to be separated areselected from the group consisting of Pd⁴⁺, Pd²⁺, Ru³⁺, Au³⁺, Au⁺, Ag⁺and Hg²⁺.
 3. A method according to claim 2 wherein the receivingsolution is any solution having properties which allow for the desiredions to be broken from said compound.
 4. A method according to claim 3wherein said receiving solution is an aqueous solution containing one ormore ions or compounds selected from the group consisting of NO₂ ⁻, SO₃²⁻, EDTA, DTPA, NTA, Br⁻ and ⁻ as well as NH₃, amines, thiourea and CN⁻.5. A method according to claim 3 wherein A is S.
 6. A method accordingto claim 5 wherein Q contains at least one electron withdrawingsubstituent selected from the group consisting of amido, aldehyde,ketone, sulfonyl, carboxyl, phenyl, I, Br, Cl, F, cyano and nitro andmixtures thereof.
 7. A method according to claim 6 wherein X is a grouphaving the formula (CH₂)_(a) (OCH₂ CHR¹ CH₂)_(b) wherein a is 3, R¹ isOH and b is
 1. 8. A method according to claim 7 wherein Q is phenyl. 9.A method according to claim 8 wherein the desired ion is Hg.
 10. Amethod according to claim 6 wherein Q is a halo substituted phenyl. 11.A method according to claim 10 wherein the desired ion is Pd.
 12. Amethod according to claim 6 wherein Q is nitro substituted phenyl.
 13. Amethod according to claim 12 wherein the desired ion is Pd.
 14. A methodaccording to claim 6 wherein Q is carboxyl substituted phenyl.
 15. Amethod according to claim 14 wherein the desired ion is Ag.
 16. A methodaccording to claim 16 wherein Q is carboxyl substituted lower alkyl. 17.A method according to claim 16 wherein the desired ion is Au.